CN1482149A - Fusible polyacrylonitrile resin - Google Patents
Fusible polyacrylonitrile resin Download PDFInfo
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- CN1482149A CN1482149A CNA021369569A CN02136956A CN1482149A CN 1482149 A CN1482149 A CN 1482149A CN A021369569 A CNA021369569 A CN A021369569A CN 02136956 A CN02136956 A CN 02136956A CN 1482149 A CN1482149 A CN 1482149A
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- crotononitrile
- polyacrylonitrile
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- acrylonitrile
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Abstract
The polyacrylonitrile resin features that the polymer molecule chain contains copolymerized crotononitrile units in 10-15 wt% and the homogeneous copolymerization of acrylonitrile units and crotononitrile units. The polymer has viscosity-average molecular weight of 2000-4000. Crotononitrile used as copolymerized monomer has one more methylene group than acrylonitrile and thus can damage the hexatomic ring structure formed with adjacent acrylonitrile monomer and lower the ring forming probability in the molecular chain. In addition, the two kinds of unsaturated olefine monomer with cyano group have very high compatibility and near reactivity ratio, and this results in the easy control of reaction, fusible polymer for fusion processing and fusion spinning to produce polyacrylonitrile fiber. The addition of the copolymerized component has no influence to the spinning performance and the physical performance of fiber.
Description
Technical field
The present invention relates to a kind of high molecular polymer, particularly polymerization single polymerization monomer is the high molecular polymer of third rare nitrile.
Background technology
Polyacrylonitrile resin is the wider superpolymer of a kind of purposes, and particularly the fibre property of acrylic resin manufacturing exactly likes wool, occupies very big proportion in the synthon production.But a defective of polyacrylonitrile resin is a fusing point (theoretical value is 319 ℃) is higher than decomposition temperature (being generally 250 ℃), therefore it can't be processed with the fused method, polyacrylonitrile fibre also can only be used the method manufacturing of solvent spinning usually, this spinning processes will use a large amount of poisonous and harmfuls or mordant solvent, must carry out the recovery and the purification of solvent in process of production, and must wash and drying etc. fiber, so complex process and environmental pollution are serious.
For many years, reduce the research of polyacrylonitrile fusing point and quite paid close attention to, and obtained gratifying progress.In prior art, more in the past is to adopt the water plasticising method of (comprising low molecular solvent plasticising), water or other low molecular solvent can make this mixture be molten state under lower temperature after polyacrylonitrile resin is soaked into, but when adopting this kind method to carry out melt-spinning, easily produce cavity filament, fracture of wire, lousiness, fiber also can exist internal capillary and surface imperfection, thereby causes fibre property to descend greatly, so also there is more problem in suitability for industrialized production.
Become the focus of exploitation fusible polyacrylonitrile resin in recent years as the chemical modification method of non-plasticizing, it is to introduce the comonomer that can form flexible chain on the polyacrylonitrile macromolecular chain, by the sequential structure of control multipolymer and the fusing point that molecular weight reduces polyacrylonitrile, to make fusible polyacrylonitrile resin.Chinese patent 94118175.8 and 94118177.4 has proposed to prepare with methacrylonitrile and acrylonitrile compolymer and methacrylonitrile, ethylenically unsaturated monomer and acrylonitrile compolymer the method for the polyacrylonitrile of melt-processable respectively, provided the fusion moment of torsion of product under 200 ℃ in the application documents, the not play-by-play of other performance.
We know, acrylonitrile unit is joined in mode end to end in the polyacrylonitrile macromolecular chain, and this makes and easily forms the cyclic amidino compound when polyacrylonitrile is heated between link units.Simultaneously, polyacrylonitrile side group CN polarity owing to molecular chain in heat-processed is bigger, make intermolecular reactive force very strong, when the energy of external force also is not enough to overcome the intermolecular time spent of doing, the primary valence chain of macromolecular chain is earlier destroyed before a part of fusion, produce thermolysis, it is generally acknowledged that this is the basic reason that the polyacrylonitrile resin fusing point is higher than decomposition temperature.Second comonomer that fusible polyacrylonitrile resin adopted that existing chemical modification method makes fails to address this problem from structure, therefore can not obtain very ideal effect when being used for melt-spinning manufactured polyacrylonitrile fibre.
Summary of the invention
The invention provides the fusible polyacrylonitrile resin that a kind of new employing chemical modification method makes, technical problem to be solved is that second comonomer that this polyacrylonitrile resin is introduced can reduce in the polyacrylonitrile molecular chain probability of Cheng Huan between link units, resin has tangible fusing point, has good flowing property after the heating, applicable to general melt-processed and melt-spinning.
Below be the technical scheme that the present invention solves the problems of the technologies described above:
A kind of polyacrylonitrile resin is characterized in that containing the crotononitrile copolymerization units of 10～15wt%, the even copolymerization of acrylonitrile unit and crotononitrile unit in this polymer molecular chain.
The viscosity-average molecular weight of polymkeric substance is generally 2000～6000.
Above-mentioned polyacrylonitrile resin generally no longer needs other to improve the second flexible monomer when being used to make polyacrylonitrile fibre, but in order to obtain good dyeing behavior, the 3rd monomer that is used for dyeing, modifying will need.Therefore, also can contain the rare sodium sulfonate copolymerization units of methyl-prop in the above-mentioned polymer molecular chain, its content is 0.2～1.0wt%.
The manufacturing of above-mentioned polyacrylonitrile resin can be adopted conventional suspension polymerization, and processing condition are also identical with the method for making conventional polyacrylonitrile.Usually temperature of reaction is 50～100 ℃, and the temperature height helps the raising of reaction conversion ratio, but too high, wastes energy.Preferably should be controlled at 70～80 ℃.
Monomeric input concentration can be 10～50wt%, and higher monomer concentration helps the raising of reaction conversion ratio, but too high input concentration can make the viscosity of reaction system become big, and is mobile poor, operational difficulty.Best input concentration is 20～30wt%.
The initiator that copolyreaction is used can adopt water miscible oxygenant and/or reductive agent, is the ideal oxygenant as Potassium Persulphate, ammonium persulphate, sodium chlorate, hydrogen peroxide, and Sodium Pyrosulfite, S-WAT, sodium bisulfite etc. are the ideal reductive agents.The add-on of initiator can be decided according to processing requirement, and weight ratio general and the monomer total amount is (0.05～10): 100, be preferably (0.5～1.5): 100.
The chain-transfer agent of molecular weight of being used to adjust adopts thio-alcohol and different alkanols compound usually, as Virahol and dodecyl mercaptans etc.The chain-transfer agent add-on also is decided by processing requirement, and weight ratio general and the monomer total amount is (0.02～10): 100, be preferably (2.0～4.0): 100.
In copolyreaction, can also add necessary auxiliary agent or additive, for example other properties-correcting agent such as light-colored agent, stablizer, antioxidant, delustering agent.
Polymerization can be adopted intermittent type, semi continuous, continuous process, and the reaction times of batch process is controlled according to transformation efficiency, generally can be in 1～20 hour scope, and preferred 3～6 hours.
The slurries that polyreaction obtains after filtration, washing, drying, just obtain white granular or Powdered acrylic resin product.
Selecting crotononitrile for use is key point of the present invention as the modified copolymer monomer of polyacrylonitrile, because crotononitrile has been Duoed a methylene than third rare nitrile, destroy it and adjacent third rare nitrile unit forms the structure of six-ring, thereby reduced in the whole polyacrylonitrile molecular chain probability of Cheng Huan between link units.In addition, comonomer all is ethylenic unsaturation hydrocarbon monomers of cyano-containing, so both consistencies are very good, and the reactivity ratio of copolyreaction is close, and reaction is control easily.The polymkeric substance melt-processable that obtains, or with melt-spinning manufactured polyacrylonitrile fibre, can not influence the physicals of spinning properties and fiber because of the adding of copolymerization component.
Embodiment [embodiment 1～7]
In the reactor that has reflux exchanger, electric mixer and electric heating temperature controller, be that medium carries out suspension polymerization with water.Drop into vinyl cyanide/crotononitrile mix monomer by the composition in the table 1 in the mode that drips charging, monomer feed concentration is 30%, the add-on of oxygenant ammonium persulphate is that the weight ratio of oxygenant and monomer total amount is 1: 100 in the initiator, reductive agent Sodium Pyrosulfite add-on is that the weight ratio of reductive agent and monomer total amount is 1: 100, according to the molecular weight of product requirement, add an amount of molecular weight regulator Virahol.Temperature of reaction is 75 ℃, after 3 hours reaction mixture is filtered, washs, then in vacuum drying oven in 80 ℃ dry 10 hours down, obtain white powder acrylic resin product.
The viscosity-average molecular weight and the fusing point that obtain the acrylic resin product are listed in table 2, and fusing point is measured with the micro-thermal analyzer of WRX-1S, are fusing point with the temperature during the whole fusion of polymkeric substance on the instrument.Viscosity-average molecular weight adopts Ubbelohde viscometer to measure specific viscosity η
Sp, obtain by conversion then.Table 1.
Table 2.
| Crotononitrile content (wt%) in the monomer total amount | |
| Embodiment 1 | ???????10 |
| Embodiment 2 | ???????12 |
| Embodiment 3 | ???????13 |
| Embodiment 4 | ???????14 |
| Embodiment 5 | ???????15 |
| Embodiment 6 | ???????15 |
| Embodiment 7 | ???????15 |
| Viscosity-average molecular weight (* 10 4) | Fusing point (℃) | |
| Embodiment 1 | ??????3.83 | ????245 |
| Embodiment 2 | ??????3.07 | ????238 |
| Embodiment 3 | ??????3.12 | ????231 |
| Embodiment 4 | ??????3.98 | ????225 |
| Embodiment 5 | ??????3.55 | ????221 |
| Embodiment 6 | ??????2.10 | ????205 |
| Embodiment 7 | ??????5.85 | ????270 |
Because other parts are basic identical with the manufacturing of general polyacrylonitrile in the polymerization technique, this knows for those skilled in the art's right and wrong Changshu, so embodiment is no longer enumerated respectively this.
Claims (3)
1, a kind of polyacrylonitrile resin is characterized in that containing the crotononitrile copolymerization units of 10～15wt%, the even copolymerization of acrylonitrile unit and crotononitrile unit in this polymer molecular chain.
2, polyacrylonitrile resin according to claim 1, the viscosity-average molecular weight that it is characterized in that described polymkeric substance is 2000～6000.
3, polyacrylonitrile resin according to claim 1 and 2 is characterized in that containing the rare sodium sulfonate copolymerization units of methyl-prop in described polymer molecular chain, its content is 0.2～1.0wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021369569A CN1189491C (en) | 2002-09-12 | 2002-09-12 | Fusible polyacrylonitrile resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021369569A CN1189491C (en) | 2002-09-12 | 2002-09-12 | Fusible polyacrylonitrile resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1482149A true CN1482149A (en) | 2004-03-17 |
| CN1189491C CN1189491C (en) | 2005-02-16 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021369569A Expired - Fee Related CN1189491C (en) | 2002-09-12 | 2002-09-12 | Fusible polyacrylonitrile resin |
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| CN (1) | CN1189491C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100348660C (en) * | 2004-07-29 | 2007-11-14 | 中国石化上海石油化工股份有限公司 | Combination of Fusible polyacryonitrile resin in low melting point |
| CN100348659C (en) * | 2004-07-29 | 2007-11-14 | 中国石化上海石油化工股份有限公司 | Fusible polyacrylonitrile resin in low melting point |
| CN100354359C (en) * | 2004-07-29 | 2007-12-12 | 中国石化上海石油化工股份有限公司 | Fusible polyacrylonitrile resin in low melting point |
| CN100354362C (en) * | 2004-07-29 | 2007-12-12 | 中国石化上海石油化工股份有限公司 | Method for lowering melting point of fusible polyacrylonitrile resin through additive |
| CN100354361C (en) * | 2004-07-29 | 2007-12-12 | 中国石化上海石油化工股份有限公司 | Method for lowering melting point of fusible polyacrylonitrile resin |
| CN100354360C (en) * | 2004-07-29 | 2007-12-12 | 中国石化上海石油化工股份有限公司 | Method for lowering melting point of fusible polyacrylonitrile resin |
-
2002
- 2002-09-12 CN CNB021369569A patent/CN1189491C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100348660C (en) * | 2004-07-29 | 2007-11-14 | 中国石化上海石油化工股份有限公司 | Combination of Fusible polyacryonitrile resin in low melting point |
| CN100348659C (en) * | 2004-07-29 | 2007-11-14 | 中国石化上海石油化工股份有限公司 | Fusible polyacrylonitrile resin in low melting point |
| CN100354359C (en) * | 2004-07-29 | 2007-12-12 | 中国石化上海石油化工股份有限公司 | Fusible polyacrylonitrile resin in low melting point |
| CN100354362C (en) * | 2004-07-29 | 2007-12-12 | 中国石化上海石油化工股份有限公司 | Method for lowering melting point of fusible polyacrylonitrile resin through additive |
| CN100354361C (en) * | 2004-07-29 | 2007-12-12 | 中国石化上海石油化工股份有限公司 | Method for lowering melting point of fusible polyacrylonitrile resin |
| CN100354360C (en) * | 2004-07-29 | 2007-12-12 | 中国石化上海石油化工股份有限公司 | Method for lowering melting point of fusible polyacrylonitrile resin |
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| Publication number | Publication date |
|---|---|
| CN1189491C (en) | 2005-02-16 |
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Granted publication date: 20050216 Termination date: 20100912 |